无机材料学报 ›› 2024, Vol. 39 ›› Issue (6): 634-646.DOI: 10.15541/jim20230530
王伟明1(), 王为得1,2(
), 粟毅1, 马青松1, 姚冬旭3, 曾宇平3(
)
收稿日期:
2023-11-14
修回日期:
2024-01-15
出版日期:
2024-06-20
网络出版日期:
2024-01-22
通讯作者:
王为得, 助理研究员. E-mail: nudtwwd@163.com;作者简介:
王伟明(1995-), 男, 博士研究生. E-mail: wangweiming1207@163.com
基金资助:
WANG Weiming1(), WANG Weide1,2(
), SU Yi1, MA Qingsong1, YAO Dongxu3, ZENG Yuping3(
)
Received:
2023-11-14
Revised:
2024-01-15
Published:
2024-06-20
Online:
2024-01-22
Contact:
WANG Weide, associate professor. E-mail: nudtwwd@163.com;About author:
WANG Weiming (1995-), male, PhD candidate. E-mail: wangweiming1207@163.com
Supported by:
摘要:
功率半导体器件高电压、大电流、高功率密度的发展趋势, 对器件中陶瓷基板的散热能力和可靠性提出了更高的要求, 兼具高热导率和优异力学性能的氮化硅陶瓷作为功率半导体器件的首选散热基板材料受到了广泛关注。目前氮化硅陶瓷热导率的实验值与理论值存在较大差距, 高温、长时间保温的制备条件不仅会使晶粒过分长大,削弱其力学性能, 而且会造成成本高企, 限制了其规模化应用。晶格氧缺陷是影响氮化硅陶瓷热导率的主要因素, 通过筛选非氧化物烧结助剂降低体系中的氧含量, 调节液相的组成和性质并构建“富氮-缺氧”的液相, 调控液相中的溶解析出过程, 促进氮化硅陶瓷晶格氧的移除及双峰形貌的充分发育, 从而实现氮化硅陶瓷热导率-力学性能的协同优化是目前研究的热点。本文基于元素分类综述了当前国内外开发的非氧化物烧结助剂体系, 着重从液相调节和微观形貌调控的角度介绍了非氧化物烧结助剂改善氮化硅陶瓷热导率的作用机理, 分析了晶粒发育、形貌演变规律和晶格氧移除机制, 并展望了高导热氮化硅陶瓷的未来发展前景。
中图分类号:
王伟明, 王为得, 粟毅, 马青松, 姚冬旭, 曾宇平. 以非氧化物为烧结助剂制备高导热氮化硅陶瓷的研究进展[J]. 无机材料学报, 2024, 39(6): 634-646.
WANG Weiming, WANG Weide, SU Yi, MA Qingsong, YAO Dongxu, ZENG Yuping. Research Progress of High Thermal Conductivity Silicon Nitride Ceramics Prepared by Non-oxide Sintering Additives[J]. Journal of Inorganic Materials, 2024, 39(6): 634-646.
图1 功率半导体器件封装示意图[1]
Fig. 1 Schematic of typical packaging of power semiconductor device[1] (1200 V, chip area 9 mm×9 mm, encapsulated with Al2O3 DCB substrate)
Material | Thermal conductivity/ (W·m-1·K-1) | Fracture toughness/ (MPa·m1/2) | Bending strength/ MPa |
---|---|---|---|
Al2O3 | 18-24 | 3.5-4.0 | 300-400 |
AlN | 150-270 | 3.0-3.5 | 220-310 |
ZTA | 28 | 4.5 | 650 |
Si3N4 | 80-177 | 6.5-7.5 | 600-800 |
表1 常用陶瓷基板材料特性[2]
Table 1 Properties of ceramic substrate materials[2]
Material | Thermal conductivity/ (W·m-1·K-1) | Fracture toughness/ (MPa·m1/2) | Bending strength/ MPa |
---|---|---|---|
Al2O3 | 18-24 | 3.5-4.0 | 300-400 |
AlN | 150-270 | 3.0-3.5 | 220-310 |
ZTA | 28 | 4.5 | 650 |
Si3N4 | 80-177 | 6.5-7.5 | 600-800 |
图3 玻璃相体积分数、晶界膜厚度(δ)、晶粒尺寸对β-Si3N4热导率的影响[13]
Fig. 3 Effects of volume fraction of glassy phase, grain- boundary film thickness(δ), and grain size on the thermal conductivity of β-Si3N4[13]
图7 硅酸盐液相中氟原子的解聚机理[22]
Fig. 7 Depolymerization mechanism of F atom in silicate melts[22] (a) F atom breaks the network structure by replacing the bridging oxygen atoms; (b) Solute atom solution-diffusion-precipitation mechanism during liquid-phase sintering in samples YOMO and YFMF; (c) Free energy barriers overcome by solute atoms in melts Y-Si-O-N and Y-Si-O-N-F; (d) Mechanism of solute drag effect on grain boundary migration
图8 添加不同助剂的氮化硅陶瓷气压烧结(GPS)后的SEM形貌[24]
Fig. 8 SEM morphologies of the polished surfaces of Si3N4 ceramics after gas pressure sintering (GPS) with different additives added[24] (a) MgO-doped for 2 h; (b) MgO-doped for 48 h; (c) MgSiN2-doped for 2 h; (d) MgSiN2-doped for 48 h
图9 添加Y2O3 (a)和Y2Si4N6C (b)烧结助剂的氮化硅陶瓷样品的HRTEM照片[31]
Fig. 9 Typical HRTEM images of Si3N4 ceramics added with Y2O3 (a) and Y2Si4N6C (b) as additives[31]
图14 添加ZrO2、ZrH2的氮化硅陶瓷STEM-EDS表征[47]
Fig. 14 STEM-EDS characterizations of Si3N4 ceramics with the addition of ZrO2 and ZrH2[47] (a, d) Bright-field TEM images for Si3N4 ceramics with the addition of (a) ZrO2 and (d) ZrH2; (b, e) Elements distribution for Si3N4 ceramics with the addition of (b) ZrO2 and (e) ZrH2; (c) EDS analysis of the marked points in (a, d) images; (f) HRTEM image presenting the grain boundary film marked by the red rectangle in (d) image
图15 未添加(a, c)和添加(b, d)含C埋粉的氮化后样品微观形貌(a, b)和气压烧结后氮化硅微观形貌(c, d)[57]
Fig. 15 SEM images on the fracture surfaces of nitrided samples (a, b) and post-sintered samples (c, d) without (a, c) and with (b, d) graphite powder bed addition[57]
图16 PDA涂层的TEM照片及碳-氮化硅核壳结构示意图[59-60]
Fig. 16 TEM images of PDA-coated powder and schematic of Si3N4-C core-shell structure[59-60] (a, e) Overall morphologies of PDA-coated (a) and PDA-free (e) powder; (b, f) Partial magnified images of (a, e), respectively; (c, g) O distributions of PDA-coated (c) and PDA-free (g) powder; (d, h) Si and N distributions of PDA-coated (d) and PDA-free (h) powder; (i) Schematic of Si3N4-C core-shell structure
图17 氮化硅陶瓷烧结过程的(a)收缩行为和致密化机理, 以及(b)β相比例与相对密度的关系[62]
Fig. 17 (a) Shrinkage behaviors and densification mechanism of Si3N4 ceramics during sintering, and (b) relationship between β phase ratio and relative density[62]
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摘要 |
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